Materials Letters xxx (xxxx) xxx

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

One-pot synthesis of novel nanoparticle-anchored silver nanowires with

abundant hotspots for high-performance UV photodetector based on
ZnS nanobelts
Guangyuan Wang, Xianquan Meng *
School of Physics and Technology, Wuhan University, Wuhan 430072, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: A high-performance ZnS-based UV photodetector (PD) with novel nanoparticle-anchored silver nanowires (NP-
Particles anchored Ag NWs) networks as enhanced platform is reported. The materials’ d-spacing and crystallite size were
Nanosized calculated using XRD date which are in good agreement with HRTEM results. Benefitting from the plasmonic gap
Silver nanowires networks
effects in the NP-NW junctions, the fabricated photodetector yields a fast response speed (tr = 0.04 s and td =
Hotspots
ZnS nanobelts
0.05 s), decent on/off ratio (4 8 2), high responsivity (1.8 × 103 A/W) and excellent detectivity (3.3 × 1013
Sensors Jones). The strategy presented in this work may be instructive for designing high-performance optoelectronic
devices.

1. Introduction good conductive electrodes as well as the excellent plasmonic nano­

Due to the high transparency, god conductivity and solution pro­
cessability, Ag NWs are emerging as an excellent candidate to the next-
generation transparent conducting electrodes [1]. It should also be
noted that Ag NWs with strong surface plasmon resonance (SPR) have
been widely applied as plasmonic nanostructures for high-performance
optoelectronic devices such as photodetectors [2]. The introduction of
plasmonic metallic nanostructures (e.g., Ag NW and NP) to improve the
performance of photodetectors is due to the nanoscale light confinement
and high intensity enhancement on the metallic nanostructures’ surface
upon the excitation of SPR [3]. Compared to a single plasmonic NW or
NP that can yield limited near-filed intensity enhancement, when plas­
monic NPs and NWs are separated by the covered PVP a tiny distance,
the formed NP-NW nanogaps could provide giant intensity enhancement
known as plasmonic gap effects. Here, we consider using plasmonic gap
effects to fabricate high-performance photodetectors, and such an
attempt hasn’t been seen in photodetection field. Therefore, Novel NP-
anchored Ag NWs with abundant hotspots as well as high-quality ZnS
nanobelts (NBs) have been successfully synthesized through one-step
method, in which ZnS NBs are chosen as active layer because of their
large surface-to-volume ratio and suitable band-gap (~3.77 eV) corre­
sponding to the SPR position of Ag material in UV region. Taking
advantage of the NP-anchored Ag NWs simultaneously serving as the
structures, the fabricated ZnS-based UV photodetector is indeed great
figures-of-merit, which may be helpful for investigating high-
performance photodetectors.
2. Experimental section
For the synthesis of Ag NWs, 0.3 g polyvinylpyrrolidone (PVP, Mw =
1300000) and 0.2 g AgNO3 were dissolved completely in 50 mL ethylene
glycol (EG). After adding 10 μM FeCl3 of EG solution, the obtained
mixture was sealed in a 75 mL vial to perform a hydrothermal reaction at
130 ◦ C for 6 h. For the synthesis of ZnS NBs, 0.5 g ZnS powder (99.99%)
was in the center of furnace and Si substrate with 5 nm Au film was
placed at the downstream about 12 cm. The reaction was maintained at
980 ◦ C for 60 min at atmospheric pressure, during which Ar of 200 sccm
flow rate was introduced as carrying gas. For the fabrication of photo­
detectors, the Ag NWs were deposited on a polytetrafluoroethylene
(PTFE) membrane through vacuum filtration and the resulting Ag NWs
film was cut a channel (20 μm in width) using the Merkur blade. Then
ethanol dispersions of ZnS NBs (1 mg/mL) with 4 μL was dropped right
in the middle of channel to connect the drain and source of Ag NWs
electrodes. Smooth Ag NWs with a size similar to as-synthesized Ag NWs
were purchased from Nanjing XFNANO Materials Tech Co., Ltd. The
characterizations of scanning electron microscopes (SEM), transmission

* Corresponding author.
E-mail address: mengxq@whu.edu.cn (X. Meng).

https://doi.org/10.1016/j.matlet.2021.131306
Received 27 September 2021; Received in revised form 25 October 2021; Accepted 15 November 2021
Available online 18 November 2021
0167-577X/© 2021 Elsevier B.V. All rights reserved.

Please cite this article as: Guangyuan Wang, Xianquan Meng, Materials Letters, https://doi.org/10.1016/j.matlet.2021.131306
G. Wang and X. Meng
Fig. 1. The SEM, HRTEM and XRD results of (a–d) NP-anchored Ag NWs and (e–h) ZnS NBs.
Fig. 2. The FDTD simulations of (a, d) 25 nm Ag nanoparticle, (b, e) 120 nm Ag Nanowire and (c, f)1 nm gap at NP-NW junction.
electron microscope (TEM), X-ray diffraction (XRD) and photoelectric
performances are performed in Zeiss SIGMA, JEM-F200, Xpert Pro and
Keithley 4200-SCS, respectively. The 50 W Xenon lamp with several
optical filters are used as light sources which intensities were calibrated
with a silicon photodiode.
3. Results and discussion
Fig. 1a, b shows SEM images of as-synthesized Ag NWs with low- and
high-magnification, respectively. The Ag NWs exhibit a very uniform
length of 80 μm and an average diameter of ~120 nm. Curiously
enough, the surfaces of as-synthesized Ag NWs are rather rough and
natively anchored with numerous Ag NPs (~25 nm in diameter) which
are the seeds that failed to grow into Ag NWs. Fig. 1c depicts the HRTEM
image of a NP-NW junction, both the surfaces of Ag nanoparticle and
nanowire are covered with PVP in the thickness of 1 nm, and the
measured interplanar d-spacing of 0.236 nm is corresponding to the 111
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Materials Letters xxx (xxxx) xxx
planes of face-centered cubic Ag. The inset in the top left corner is the
selected area electron diffraction (SAED) pattern of this recline Ag
nanowire, which suggests the Ag nanowire grows along [1 1 0] direction.
Fig. 1d shows the XRD pattern of as-synthesized Ag NWs, which verifies
that the Ag NWs are in face-centered cubic phase (JCPDS No.04-0783).
Using 111 diffraction peak, the d-spacing and crystallite size have been
calculated to be 0.236 and 31.9 nm, respectively (inserted table). The
first value is the same as the measured one from HRTEM image, and the
second value is comparable to the image-determined size of the nano­
particles [4]. Fig. 1e, f shows SEM images of as-prepared ZnS NBs with
length up to hundreds of microns and width around 10 µm, respectively.
As shown in HRTEM image (Fig. 1g), the marked interplanar d-spacings
of 0.33 and 0.63 nm correspond to the 01 1 0 and 0001 planes of a
hexagonal wurtzite ZnS. The corresponding fast Fourier transformation
(FFT) pattern in the inset reveals that ZnS NBs grow in the [01 1 0]
orientation. Fig. 1h shows the XRD diffractogram of ZnS NBs, which
could be indexed with a standard pattern (JCPDS No.36-1450) of ZnS in
G. Wang and X. Meng Materials Letters xxx (xxxx) xxx

Fig. 3. Schematic of fabrication process for NP-anchored Ag NWs PD.

Fig. 4. The I-V curves, I-t curve and response speed of (a–c) NP-anchored Ag NWs PD and (d–f) smooth Ag NWs PD; The on/off ratio, responsivity and detectivity
compared between the two PDs at 5 V bias.

hexagonal wurtzite phase. Corresponding to aforementioned 01 1 0 and
0001 planes, the calculated d-spacings are 0.331 and 0.625 nm respec­
tively, which are in good agreement with the measured values from
HRTEM. And the calculated crystallite sizes are 65.9 and 50.3 nm
respectively, which reflects the uniform orientation of as-prepared ZnS
NBs in a relatively large size.
Based on geometric sizes of NP-anchored Ag NWs. we have carried
out the finite-difference time-domain (FDTD) simulations in free space
to determine the near-filed intensity enhancement in a nanoparticle,
nanowire and NP-NW junction, respectively. Fig. 2a shows the scat­
tering, absorption and extinction coefficients of 25 nm Ag nanoparticle,
in which the SPR appears at 360 nm. Fig. 2d shows the near-field in­
tensity distributions in x-y plane of the nanoparticle at resonance. The
intensity of the electric filed in the surface is up to 90 times that of the
incident light. As shown in Fig. 2b, e, the resonance peak of Ag nanowire
in 120 nm diameter is observed at 350 nm and the intensity is increased
by highest a factor of ~11. Fig. 2f shows near-field intensity distribu­
tions in x-z plane around a 1 nm gap of NP-NW junction (as depicted in

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G. Wang and X. Meng Materials Letters xxx (xxxx) xxx

Table 1
Comparison of performances between ZnS-based UV photodetectors.
Photodetector Light source Bias (V) On/off ratio Rλ (A/W) D* (Jones) Rise/decay (s) Reference
2 3
ZnS nanobelts 300 nm (1.2 mW/cm ) 1 5 1.9 × 10 – 2.8/7.5 [5]
ZnS nanotubes Xenon lamp (40 mW/cm2) 0 19,173 2.56 1.67 × 1010 0.09/0.07 [6]
ZnS microspheres 365 nm (8.89 × 10− 4 W) 10 1.35 8.94 × 10− 5 6.51 × 108 0.153/0.206 [7]
ZnS thin film/p-Si 350 nm (230 μW/cm2) 0 – 6.9 × 10− 2 4.29 × 1012 0.35/0.51 [8]
ZnS nanobelts 365 nm (2.56 mW/cm2) 5 482 1.8 × 103 3.3 × 1013 0.04/0.05 This work

Fig. 2c). the largest intensity enhancement is 1600 times which is much
larger than that of a single Ag nanoparticle and nanowire.
Fig. 3 illustrate the fabrication process for NP-anchored Ag NWs PD.
During the photoresponse test, the devices were illuminated with the UV
light of 365, 380 and 405 nm, which have the light intensities to be 2.56,
2.67 and 3.19 mW/cm2, respectively. Fig. 4a–c shows the wavelength-
dependent I-V curves, time-dependent conductance response and
response speed of NP-anchored Ag NWs PD. As a comparison, those
records of the smooth Ag NWs PD are depicted in Fig. 4d–f. Both PDs
have an excellent UV photoresponse and good reproducibility. Never­
theless, the response speed of NP-anchored Ag NWs PD (tr = 0.04 s and
td = 0.05 s) is faster than that of smooth Ag NWs PD (tr = 0.11 s and td =
0.13 s). There are three key parameters that can be further evaluated for
the performance of photodetectors, namely on/off ratio (Iph/Idark),
responsivity (Rλ = Iph/(PA)) and specific detectivity (D* = RλA1/2/
(2qIdark)1/2), where Iph, Idark, P, A and q are the net photocurrent, dark
current, incident light intensity, effective area and absolute value of
electron charge, respectively. As shown in Fig. 4g–i, NP-anchored Ag
NWs PD shows superior photoresponse performance in all the terms of
on/off ratio, responsivity and detectivity. Notably, A highest on/off ratio
of 482, responsivity of 1.8 × 103 A/W and specific detectivity of 3.3 ×
1013 Jones are obtained in NP-anchored Ag NWs PD under the illumi­
nation of 365 nm light at a bias of 5 V. And those values as well as above-
mentioned response times are great among many ZnS-based UV photo­
detectors (as summarized in Table 1). As can be noticed from Table 1,
the response times of our photodetector are generally one order of
magnitude shorter than those reported in other literatures. Especially,
the rise time is significantly short, leading a fast response for our
photodetector. In the present work, the detectivity and responsivity are
also more than several orders higher than recently reported values by
other authors on different device configurations [6–8]. High on/off ratio
suggests the significant increase in photocurrent with respect to dark
current which shows good switching characteristics of the present
fabricated photodetector. Comparing the response times, on/off ratio,
responsivity and detectivity results with previously published works, it
is apparent that our photodetector has excellent comprehensive
performance.
4. Conclusions
In summary, we have demonstrated a high-performance UV photo­
detector with ZnS NBs as active layer and novel NP-anchored Ag NWs as
efficient plasmonic electrodes. The crystal information of the materials
is well revealed through the comparative study of HRTEM and XRD.
FDTD simulation shows that there is 1600 times near-field intensity
enhancement in the hotspot of the NP-NW junction. The fabricated
photodetector exhibits excellent comprehensive performance compared
with the recent reports, so we are convinced that NP-anchored Ag NWs
provide more powerful building blocks for high-performance
photodetectors.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
This work was financially supported by the National Natural Science
Foundation of China (Grant Nos. U1631110).
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